Material for chromatography

ABSTRACT

Granulated products are provided and include carbonaceous particles and a carbonized agent or binder. The agent or binder is preferably a synthetic resin, pitch component, or mixture thereof. Packing materials for packing columns used in chromatographic separations are also provided as are methods of chromatographic separation using the materials. In addition, methods are provided to provide a variety of different types of carbonaceous products. A variety of chemical groups can be, prior to heat-treatment and/or thereafter, attached to the granules to form modified granules.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to a packing material forchromatographic separations and to a method of manufacturing the same.More particularly, the present invention relates to a packing materialfor liquid chromatography produced by mixing a carbon product, such ascarbon black with a synthetic resin and/or a pitch component,granulating the mixture, and heat treating the resultant granules. Thepresent invention also relates to methods of chromatographic separationthat employ the granules.

[0002] Conventionally, packing materials for liquid chromatography haveincluded silica gel materials and synthetic resin-based materials.However, problems such as chemical stability, including solubility, haveresulted in silica gel-based materials exhibiting poor durability as apacking material.

[0003] In chromatography and other separation methods, there is acertain amount of selectivity that is necessary in order for thestationary phase to separate the various components in a mixture. Forthis reason, carbon products, such as carbon black, have not been usedas a standard stationary phase in separation systems because carbon is astrong non-specific adsorbent. This has been disappointing in the past,because carbon products, otherwise, would have many advantages overcommercially available adsorbents. For instance, there are no corrosionproblems with carbon products nor are there any swelling problems withcarbon products. In addition, carbon products can be subjected to largetemperature ranges and/or extreme pressures which would be beneficialfor certain types of adsorptions, such as temperature swings used insome types of chromatography. In addition, with certain separationprocesses used in the production of biopharmaceuticals for clinicalapplications, the sterilization requirements or recommendations providefor the use of hot sodium hydroxide. With such sterilization procedures,the current separation devices such as silica columns, cannot be used.Further, the polymeric columns such as cellulose polymers, arechemically but not physically stable to such sterilization treatments.

[0004] U.S. Pat. No. 5,270,280 relates to the use of carbon blackpacking materials for liquid chromatography, wherein the carbon blackshave specific dimensional ratios, specific particle diameters andsurface areas, and specific micropore volumes. The patent isincorporated herein in its entirety by reference. The methods of makingthe packing material according to U.S. Pat. No. 5,270,280 includegranulating a carbon black-containing mixture and heat-treating thegranules at a high temperature in the range of from 800° C. to about3000° C., in an inert atmosphere. The high temperature heat-treatment ismost likely necessary to carbonize and graphitize the binder material inorder to form a graphitic layer. According to the patent, if thetemperature is below 800° C., the graphitization of the binder is notsufficient, resulting in the packing material having insufficientstrength. While the patent describes the packing material as providingimproved mechanical durability and separating characteristics, a needstill exists for an improved liquid chromatography packing material thathas improved mechanical durability and improved separating properties.

[0005] It is desired to provide an improved liquid chromatographicpacking material and a method of producing such a material which doesnot require a high temperature heat-treatment or graphitization step.

[0006] In addition, it is desired to provide a method of chromatographicseparation that provides improved separation of sample components.

SUMMARY OF THE INVENTION

[0007] The present invention relates to an improved chromatographicpacking material made of carbonaceous particle-containing granulespreferably having at least one organic group attached thereto. Thegranules include carbonaceous particles and the carbonized product of acarbonizable synthetic resin, pitch component, or both. Preferredgranules include carbon black particles having attached organic groupsand a carbonized synthetic resin, pitch component, or both.

[0008] The present invention further relates to a process for making thepacking material of the present invention and includes: mixingcarbonaceous particles with at least one synthetic resin, pitchcomponent, or both, and with at least one organic or aqueous solvent, toform a mixture; granulating the mixture to form granules; heating thegranules at a relatively low temperature of from about 400° C. to lessthan 800° C. to carbonize the synthetic resin, pitch component, or both,and to evaporate the solvent. Once formed, the packing material can befurther customized for specific uses by attaching an organic group orgroups to the carbon surface.

[0009] The carbonized synthetic resin, pitch component, or both,preferably acts to strongly bind the carbonaceous particles into astrong granule, very differently than the temporary binding action ofpelletizing or binding agents designed to facilitate ready dispersal ofcarbon black particles from a pelletized carbon black.

[0010] The packing materials of the present invention preferably exhibitexcellent mechanical durability and preferably provide improvedseparating abilities in chromatographic separation applications. Thesurface-modified granular packing materials of the present invention areparticularly useful in liquid chromatographic separation applications.

[0011] Additional features and advantages of the present invention willbe set forth in part in the description that follows, and in part willbe apparent from the description, or may be learned by practice of thepresent invention. The objectives and other advantages of the presentinvention will be realized and attained by means of the elements andcombinations particularly pointed out in the description and appendedclaims.

[0012] It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are intended to provide further explanation of thepresent invention, as claimed.

BRIEF DESCRIPTION OF THE DRAWING

[0013]FIG. 1 is a microphotograph (at 5,000× magnification) ofchromatographic packing materials of the present invention.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0014] The present invention relates to a chromatographic packingmaterial. The carbonaceous particles are preferably bound together withthe carbonized product (e.g., binder) of at least one synthetic resin,at least one pitch component, or both.

[0015] The carbonaceous particles that can be treated to form thepacking material of the present invention are preferably selected fromgraphite powder, graphite fibers, carbon fibers, carbon cloth, vitreouscarbon products, activated carbon products, and carbon black. Apreferred carbonaceous particulate material is carbon black. Inaddition, the carbonaceous particles can include, but are not limitedto, carbon aerogels, pyrolized ion exchange resins, pyrolized polymerresins, meso carbon microbeads, pelleted carbon powder, nanotubes,buckey balls, silicon-treated carbon black, silica-coated carbon black,metal-treated carbon black, densified carbon black, activated carbon orother carbonaceous material obtained by the pyrolysis of cellulosic,fuel oil, polymeric, or other precursors and combinations thereof oractivated versions thereof The carbonaceous particles can also include,but are not limited to, material obtained by the compaction of smallcarbon particles and other finely divided forms of carbon as long as thecarbonaceous particles have the ability to adsorb at least one adsorbateand is preferably capable of being chemically modified in accordancewith the present invention. The carbonaceous particles can also be awaste product or by-product of carbonaceous material obtained bypyrolysis.

[0016] In addition, the carbonaceous particles can be an aggregatehaving at least one carbon phase and at least one silicon-containingspecies phase. The aggregate can be one or more of the aggregatesdescribed in U.S. Pat. Nos. 6,008,271; 5,977,213; 5,948,835; 5,919,841;5,904,762; 5,877,238; 5,869,550; 5,863,323; 5,830,930; 5,749,950;5,622,557; and 5,747,562. Furthermore, the aggregates described in WO98/47971; WO 96/37547; and WO 98/13418 can also be used, and each ofthese patents and publications is incorporated herein in its entirety byreference.

[0017] The carbonaceous particles can be a carbon black which is atleast partially coated with silica. Examples of such an aggregate aredescribed in U.S. Pat. No. 5,916,934 and WO 98/13428 which areincorporated herein in their entireties by reference.

[0018] Besides the above-described aggregates, the carbonaceousparticles can also be an aggregate having at least a carbon phase and ametal-containing species phase as described in PCT Publication WO98/47971 which is incorporated herein in its entirety by reference.

[0019] In addition, the aggregates and methods of making multi-phaseaggregates from U.S. Pat. Nos. 6,211,279; and 6,057,387; and U.S. patentapplication Ser. No. 09/453,419 can be used, and all of these patentsand application are incorporated herein in their entireties byreference. Additionally, the aggregates of U.S. patent application Ser.No. 60/163,716 having attached polymer groups can be used as can themodified pigments described in U.S. patent application Ser. No.60/178,257, both of which applications are also incorporated herein intheir entireties by reference.

[0020] Preferably, the carbonaceous particles are activated carbon orcarbon black capable of adsorbing an adsorbate. Commercial examples ofcarbon black include, but are not limited to, Black Pearls® 2000 carbonblack, Black Pearls® 430 carbon black, Black Pearls® 900 carbon black,and Black Pearls® 120 carbon black, all available from CabotCorporation. Commercial examples of activated carbon include Darco S51,available from Norit; Sorbonorit 3, available from Norit; and BPLactivated carbon from Calgon. The carbonaceous particles modified by theprocedures described herein may be a microporous or mesoporous activatedcarbon in granular or pellet form; a carbon black of differentstructures in fluffy or pelleted form; or any other carbonaceousparticles whose applicability to this invention is apparent to thoseskilled in the art, such as carbon fibers or carbon cloth. The choice ofcarbonaceous particles used eventually depends on a variety of differentfactors, including the application for which it is intended. Each ofthese types of carbonaceous particles has the ability to adsorb at leastone adsorbate. A variety of BET surface areas, micropore volumes, andtotal pore volumes are available depending on the desired end use of thecarbonaceous material.

[0021] The carbonaceous particles used to form the packing material ofthe present invention preferably comprise particles having an averageparticle diameter of from about 12 to about 40 nanometers (nm) prior togranulation, for example, from about 12 to about 30 nm, and a specificsurface area of from about 50 to about 550 m²/g, for example, from about80 to about 250 m²/g. A preferred particulate material is a carbon blackhaving these properties. The carbonaceous particles used to form themixture preferably have a DBP oil adsorption of from about 50 to about200 ml/100 g, for example, from about 80 to about 150 ml/100 g.

[0022] The synthetic resin and/or pitch component preferably attains afirm bonding among the carbonaceous particles and preferably acts as abinder. The synthetic resin and/or pitch component is preferably easilycarbonized by heating. Exemplary synthetic resins that can be usedaccording to the present invention include phenolic resins, furanresins, furfural resins, divinyl benzene resins, urea resins, andmixtures thereof.

[0023] If a pitch component is used, it is preferably toluene-soluble orbenzene-soluble. The pitch component is preferably a component ofpetroleum pitches, coal-tar pitches, or liquefied oil from coal.

[0024] Both a pitch component and a synthetic resin component can beused together, for example, whereby the pitch component is preferablycombined with the synthetic resin before contacting the carbonaceousparticles. The synthetic resin and pitch component mixture canpreferably be used in an amount of from about 5 parts by weight to about500 parts by weight, for example, from about 40 parts by weight to about300 parts be weight, per 100 parts by weight of carbonaceous particles.

[0025] To facilitate homogenization of the carbonaceous particles withthe synthetic resin, pitch component, or both, it is preferable todisperse the components in a suitable solvent. Preferably, the solventis aqueous as opposed to non-aqueous or solvent based. Exemplarysolvents that can be used include, but are not limited to, water,alcohols such as methanol, ethanol, propanol, or the like, organicsolvents having an aromatic group such as benzene, toluene, or the like,and general organic solvents such as acetone, methylethylketone, or thelike. With water-compatible synthetic resins, water is a preferredsolvent because of its ease of handling and processing. Preferably, thesolvent is used in an amount of from about 70 to about 400 parts byweight per 100 parts by weight of the combined carbonaceous particlesand syntheticresin/pitch component. For carbonaceous particles havingparticle diameters of from about 12 to about 30 nm, specific surfaceareas-of from about 80 to about 200 m²/g, and DBP oil adsorptions offrom about 80 to about 200 ml/100 g, about 0.60 part by weight solventcan be used, based on the weight of the carbonaceous particles.

[0026] Carbonaceous particles having organic groups attached thereto canin and of themselves be used as readily dispersible carbonaceousparticles, even in the absence of a surfactant, and are preferredaccording to some embodiments of the present invention.

[0027] According to a preferred method of the present invention, aprocess for producing a material for chromatography is provided andincludes mixing about 100 parts by weight of carbonaceous particleswith: from about 10 to about 500 parts by weight of at least one of asynthetic resin that can be carbonized by heating, and a pitchcomponent; and an organic or aqueous solvent. Preferably, from about 40to about 250 parts by weight synthetic resin and/or pitch component areused per 100 parts by weight carbonaceous particles. The mixture can beformed by any manner used to combine the components. The mixture canthen be granulated to form granules. The granulation can be accomplishedby a wet (emulsion) granulation technique or by a spray dryinggranulation technique. Any of the granulation techniques described inU.S. Pat. No. 5,270,280 can be used. The granules are then subjected toconditions sufficient to carbonize the synthetic resin and/or pitchcomponent and to evaporate the solvent. After carbonizing the granules,they can be further modified by attaching organic groups to thegranules.

[0028] The granulating method may be a spray drying granulation method,a submerged granulating method (an emulsion granulating method), or anyother suitable granulating method that results in spherical granules.According to a preferred spray granulation technique, granules areobtained from spraying a liquid mixture at an elevated temperature andevaporating, if present, the dispersing agent (e.g., surfactant) andsolvent. According to a preferred submerged granulating method, a liquidmixture is added to a heated agent that is not miscible with the liquidmixture. The contact results in the formation of spheres of the liquidmixture.

[0029] Carbonization may be performed by a heat-treatment using anytemperature sufficient for carbonization. Preferably, the heat-treatmentoccurs in an inert gas atmosphere at from about 400° C. to less than800° C., for example, at a temperature of from about 400° C. to about700° C., or 400° C. to 790° C. More preferably, the carbonizationtemperature to which the granulated carbonaceous particle-containingmaterial is heated, is in the range of from about 400° C. to about 600°C. Depending upon the particular synthetic resin and pitch componentsused, the conditions for carbonization can vary, but preferably aresufficient to carbonize the synthetic resin and/or pitch componentwithout compromising the yield and strength of the packing material.Preferably, heat-treatment occurs under a pressure of from about 1 toabout 8 kgf/cm²G though other pressures can be used.

[0030] The granulated particles obtained are preferably composite bodiescontaining the carbonaceous particles and an agent that uponcarbonization aids in forming a granule of high crush strength. Theagent preferably acts as a binder and includes the carbonized product ofa synthetic resin, pitch component, or synthetic resin/pitch componentmixture. The granules preferably have a L_(min)/L_(max) ratio of fromabout 0.75 to about 1.25, for example, a ratio of from about 0.90 toabout 1.0. A preferred L_(min)/L_(max) ratio is from about 0.95 to about1.0. The granules preferably have a particle diameter of from about 1 toabout 200 μm, a highly porous surface, a specific surface area of fromabout 10 to about 650 m²/g, preferably from about 15 to about 550 m²/g,a total micropore volume of from about 0.01 to about 2.0 ml/g,preferably 0.3 to about 2.0 ml/g, and a V₀₅/V_(1.0) ratio of about 0.4or smaller, preferably 0.2 or smaller, wherein V_(0.5) is the gasadsorption volume at a relative pressure P/P₀ of 0.5 and V_(1.0) is thenitrogen gas adsorption volume at a relative pressure P/P₀ of about 1.0at nitrogen gas adsorption isotherm. The particles preferably have aparticle size of from about 2 to about 5 microns, and other ranges belowand above this range can be made.

[0031] The granules can be surface modified by attaching (e.g.,covalently bonding) organic groups to the surface. The organic group ispreferably at least one C₁-C₁₀₀ alkyl group and/or at least one aromaticgroup, an aliphatic group, a cyclic organic group, or an organiccompound having an aliphatic portion and a cyclic portion. Preferably,the organic group is directly attached to the granules. A preferred setof organic groups which may be attached to the carbonaceous material,such as carbon black-containing granules, are organic groups substitutedwith an ionic or an ionizable group as a functional group. The ionicgroup may preferably be an anionic group or a cationic group and theionizable group may form an anion or a cation. Examples of organicgroups are described in U.S. patent application Ser. No. 09/654,182 andits continuation in part filed Aug. 31, 2001 both incorporated in theirentirety by reference herein.

[0032] Preferably, the organic group contains an aromatic group such asa phenyl or a napthyl group and a quaternary ammonium or a quaternaryphosphonium group. The aromatic group is preferably directly attached tothe carbonaceous particle-containing granule.

[0033] In one embodiment, the carbonizable binder or carbonizablesynthetic resin or carbon izable pitch component are attached ontocarbonaceous particles to form the granulated product of the presentinvention.

[0034] A combination of different organic groups is also possible. Forinstance, it is within the bounds of the present invention to attachmore than one type of organic group to the same granule or use acombination of granules, wherein some of the granules have been modifiedwith one organic group and another portion of the granules has beenmodified with a different organic group. Varying degrees of modificationare also possible, such as low weight percent or surface areamodification, or a high weight percent or surface area modification.Also, mixtures of modified carbonaceous granules and unmodifiedcarbonaceous granules can be used.

[0035] Preferably, the modified carbonaceous granules of the presentinvention, especially when the attached organic group is a phenyl ornaphthyl group having substituents like sulfonic acid, carboxylic acid,or quaternary ammonium or salts thereof, can be directly analogous topolymeric ion exchange resins. These types of carbonaceous granules ofthe present invention can have one or more of the following propertiesas compared to conventional polymeric ion exchangers:

[0036] a) higher temperature stability;

[0037] b) greater resistance to swelling; and

[0038] c) greater mechanical strength without adversely affecting uptakekinetics.

[0039] Furthermore, the modified carbonaceous granules of the presentinvention, besides being used as adsorbents, can also be used inseparations ranging from water treatment to metals separation/recovery,ion exchange, catalysis, and the like. An additional advantage of anadsorbent possessing exchangeable groups as described above is that itconfers on the granules the ability to be further surface modified usingion exchange procedures.

[0040] The granules of the present invention can be used in a number ofapplications, for example, as a stationary phase for chromatographicseparations. Typically, a chromatographic system contains a mobilephase, a stationary phase, a pumping system, and a detector. Generally,the stationary phase contains insoluble particles which are preferablyspherical and/or preferably range in size from about 2 microns to about300 microns, more preferably from about 2 to about 5 microns. The choiceof these particles depends on the physical, chemical, and/or biologicalinteractions that need to be exploited by the separation. Conventionalstationary phases, such as silica, agarose, polystyrene-divinylbenzene,polyacrylamide, dextrin, hydroxyapatite, cross-linked polysaccharides,and polymethacrylates are functionalized with certain groups in order toaccomplish the selective separation of particular chemical compoundsfrom a mixture. The precise functional groups that accomplish thisdesired specification are set forth, for instance, in Garcia, Bonen etal., “Bioseparation Process Science,” Blackwell Science (1999),incorporated herein in its entirety by reference (hereinafter “Garcia etal.”).

[0041] Another form of separation is electrophoresis which uses anapplied electric field to produce directed movement of chargedmolecules. The process is similar to chromatographic methods in that afixed barrier phase or stationary phase is used to facilitateseparation. In the present invention, electrophoresis can beaccomplished by using a stationary phase which contains the carbonaceousmaterials of the present invention.

[0042] Similarly, magnetic separations, such as magnetic bioseparations,can be accomplished using the carbonaceous materials of the presentinvention as the stationary phase.

[0043] In addition, membrane separations, such as reverse osmosis, canbe accomplished by forming the membrane such that it containscarbonaceous materials. The membrane can be formed by dispersing thecarbonaceous material in a polymer and casting the polymer mixture toform a membrane.

[0044] Generally, any separation technique which involves the use of astationary phase can be improved by the present invention. Inparticular, the stationary phase can be or can contain the carbonaceousgranules of the present invention. Upon knowing the desired chemicalcompound or species to be separated, the carbonaceous granules can betailored to be selective to the targeted chemical species by attachingan organic group or organic groups onto the carbonaceous granules tosuit the separation needed. Since many functional groups are known tocause particular selectivity in separations, these groups can beattached onto the carbonaceous granules to form the modifiedcarbonaceous granules of the present invention and achieve the desiredselectivity for separation processes.

[0045] In one embodiment, an adsorbent composition of the presentinvention contains modified carbonaceous granules capable of adsorbingan adsorbate wherein at least one organic group is attached to thecarbonaceous granules.

[0046] As a separate embodiment, the present invention further relatesto a granulated carbonaceous product which contains carbonaceousparticles and at least one binder which can be carbonizable. Thegranulated carbonaceous product in this embodiment is produced by theprocess of mixing the carbonaceous particles with at least one binderand preferably an aqueous solvent or nonaqueous solvent. The mixture isthen granulated to form granules and then the granules are heated at atemperature below the temperature to carbonize the binder that ispresent. Preferably, the granules are heated at a temperature of fromabout 150° C. to about 250° C. In this process, the uncarbonizedparticles that are formed contain a cured/crosslinked polymer binderwhich is present on the granules and are useful in such applications asadsorption and chromatography.

[0047] As indicated above, once the desired separation technique ischosen and the particular chemical species preferably known, aparticular functional group or multiple functional groups can be chosento be attached onto the carbonaceous material in order to accomplish theselectivity needed to conduct the separation process. For instance, asset forth in Garcia et al., heparin is used in the separation oflipoproteins, accordingly, heparin can be attached onto carbonaceousmaterial in order to accomplish the desired separation. Similarly, whencationic exchange processes are needed, a sulfonic acid, for instance,can be attached on a carbonaceous material and when anionic exchangesare needed, a quaternary amine can be attached onto the carbonaceousmaterial. Thus, with the present invention, and the knowledge possessedby one skilled in the art, separation techniques can be conducted usingmodified carbonaceous material to achieve the selectivity desired. Thus,the present invention provides a carbonaceous material which isresistant to corrosion, swelling, and/or extreme temperatures andpressures, but also provides the desired selectivity. In essence, thepresent invention gives the separation field the best of both worlds,namely, selectivity combined with a resilient stationary phase.

[0048] The granules of the present invention can preferably be used as apacking material or stationary phase material for chromatography. Forexample, a chromatographic column, such as a liquid chromatographiccolumn, is packed with at least the packing material of the presentinvention. Then, a sample containing two or more components to beseparated is passed, flowed, or otherwise forced through the packedcolumn. Due to the independent affinities of the sample components, andthe retention properties of the packing material with respect to theindividual sample components, chemical separation of the components isachieved as the sample passes through the packed column. The packingmaterial is also useful in gas chromatographic, high performance liquidchromatographic, solid phase extraction, and other chromatographicseparation techniques.

[0049] The present invention will be further clarified by the followingexamples, which are intended to be purely exemplary of the presentinvention.

EXAMPLE 1

[0050] Preparation of Carbonized Porous Particles (SP-1)

[0051] 600 g of Vulcan-6™ carbon black were placed inside a pin-mixer.520 g deionized water and 180 g of Rutgers-Plenco Resin 12868 wereblended together. The mixture was subsequently injected into the pinmixer while it was running at 100 rpm. After the end of the addition ofthe liquid phase, the speed of the mixer was increased to 1000 rpm andheld at that speed for 1 minute. The particles were then discharged fromthe mixer and dried at 180° C. overnight in order to both remove theexcess water and cure the phenolic resin. The particles were thenclassified by screening. The fraction held between the 120 mesh and 325mesh screens with particles sizes ranging between 45 and 125 microns wasseparated. This fraction was then placed in a tube furnace and ramped to650° C. in 4 hours and then held at 650° C. for an additional hour undernitrogen. These particles (SP-1) were found to have a BET N₂ surfacearea of 138 m²/g and a t-surface area of 61.5 m²/g.

EXAMPLE 2

[0052] Preparation of Surface Modified Carbonized Porous Particles(SP-2)

[0053] 0.76 g of sulfanilic acid were mixed with 100 ml of deionizedwater and subsequently heated to 60° C. 10 g of the SP-1 particles wereadded to the mixture and stirred for 5 minutes. Subsequently, 1.5 g of a20% solution of NaNO₂ in water were added to the mixture to initiate thetreatment reaction. The mixture was reacted at 60° C. for 1 hour andthen left to cool down to room temperature. The surface modifiedparticles (SP-2) were then filtered out of the reaction medium, washedwith a 1% NaOH solution, water, and ethanol and soxhlet extracted for 12hours in ethanol. The efficiency of the surface modification is shown bythe increase in the sulfur content of the particles after surfacemodification. The sulfur content of the starting particles SP-1 was 0.9wt % and the sulfur content of the particles after surface modificationwas 1.38%. The increase in sulfur content is due to the attachment ofbenzenesulfonate groups to the surface of the particles.

EXAMPLE 3

[0054] Preparation of Polymer Bound Porous Carbon Based Particles (SP-3)

[0055] 7.6 liters of a Cabojet-300™ aqueous dispersion of benzoic acidmodified carbon black were placed in a holding tank. 166.7 g of DynachemPhenalloy 2175 phenolic resin were mixed in. The mixture was spray driedat 110 ml/min through a 2-fluid nozzle. The dry particles werecollected, and subsequently cured at 180° C. for 4 hours under nitrogen.The resulting particles SP-3 had a BET N₂ surface area of 126.8 m²/g anda t-surface area of 106.2 m²/g.

EXAMPLE 4

[0056] Preparation of Benzenesulfonic Acid Surface Modified PolymerBound Porous Carbon Based Particles (SP-4)

[0057] 1.384 g of sulfanilic acid were mixed with 50 ml of deionizedwater in a beaker and heated to 60° C. 5 g of SP-3 particles were addedto the mixture. 2.76 g of a 20% solution of sodium nitrite in water wereadded slowly, and the mixture was left to react for 90 minutes. Thereaction mixture was filtered and the particles were reslurried andwashed with a 1% NaOH solution in water. The particles were refilteredand washed with deionized water, and subsequently washed with ethanoland tetrahydrofuran. The particles were soxhlet extracted in ethanolovernight. The starting sulfur content of the particles was 0.39 wt %.After the surface modification the sulfur content was 1.39 wt %indicating the attachment of benzenesulfonic groups.

EXAMPLE 5

[0058] Preparation of Porous Carbon Particles (SP-5)

[0059] 80 g of particles SP-3 were heated under nitrogen in a tubefurmace to 700° C. and held at that temperature for 2 hours. Theparticles were then cooled to room temperature. A SEM picture of theseparticles is shown in FIG. 1.

EXAMPLE 6

[0060] Preparation of Benzenesulfonic Acid Surface Modified PorousCarbon Particles (SP-6)

[0061] 1.384 g of sulfanilic acid were mixed with 30 ml of deionizedwater in a beaker and heated to 60° C. 5 g of SP-5 particles were addedto the mixture. 2.76 g of a 20% solution of sodium nitrite in water wereadded slowly and the mixture was left to react for 90 minutes. Thereaction mixture was filtered and the particles were reslurried andwashed with a 1% NaOH solution in water. The particles were refilteredand washed with deionized water, and subsequently washed with ethanol.The particles were soxhlet extracted in ethanol overnight. The startingsulfur content of the particles was 0.36 wt %. After the surfacemodification the sulfur content was 1.79 wt % indicating the attachmentof benzenesulfonic groups.

EXAMPLE 7

[0062] Preparation of Octadecylphenyl Surface Modified Porous CarbonParticles (SP-7)

[0063] 5.07 g of 4-octadecylaniline were mixed with 22 ml of deionizedwater, 50 g of ethanol, and 6.17 g of a 30% aqueous solution of HNO₃ ina beaker and heated to 50° C. 15 g of particles (made in a similarmanner as in Example 5, except heated under nitrogen in a tube furnaceto 900° C.) were added to the mixture. 5.07 g of a 20% solution ofsodium nitrite in water were added slowly and the mixture was left toreact for 90 minutes. The reaction mixture was filtered and theparticles were reslurried and washed with ethanol. The particles wererefiltered and washed with a sodium hydroxide solution, tetrahydrofuranand ethanol. The particles were first soxhlet extracted in ethanolovernight and then extracted in a Dionex ASE-300 extractor with ethanoland a 50/50 ethanol/tetrahydrofuran mixture and left to dry. After thesurface modification the volatile content of the particles was 7.59 wt %indicating the attachment of octadecylphenyl groups.

[0064] Other embodiments of the present invention will be apparent tothose skilled in the art from consideration of the present specificationand practice of the present invention disclosed herein. It is intendedthat the present specification be considered as exemplary only with atrue scope and spirit of the invention being indicated by the followingclaims and equivalents thereof.

1-13. (canceled).
 14. A method of chromatographic separation or solidphase extraction comprising passing a sample having components to beseparated through a plurality of granulated products comprisingcarbonaceous particles and at least one carbonized synthetic resin,carbonized pitch component, or mixtures thereof, wherein said granulatedproduct has attached at least one organic group.
 15. The method of claim14, wherein said chromatographic separation or solid phase extraction isa liquid chromatographic separation or solid phase extraction.
 16. Amethod of making carbonaceous particles-containing granules comprising:mixing carbonaceous particles with: at least one synthetic resin, pitchcomponent, or a mixture thereof; and a solvent, to form a mixture;granulating said mixture to form granules; carbonizing said granules;and attaching at least one organic group to said granules.
 17. Themethod of claim 16, wherein said granules are carbonized by heating to atemperature of from about 400° C. to less than 800° C.
 18. The method ofclaim 16, wherein said granules are heated to a temperature sufficientto carbonize the synthetic resin, pitch component, or both.
 19. Themethod of claim 16, wherein said temperature is sufficient to carbonizesaid synthetic resin, pitch component, or both, and to evaporate saidsolvent without graphitizing said granules.
 20. The method of claim 16,wherein said solvent is a non-aqueous solvent.
 21. The method of claim16, wherein said solvent is aqueous solvent.
 22. The method of claim 16,wherein said mixture comprises a pitch component and said pitchcomponent is a toluene-soluble pitch component, a benzene-soluble pitchcomponent, or a combination thereof.
 23. The method of claim 16, whereinthe process used to granulate said mixture is spray drying.
 24. Themethod of claim 20, wherein said pitch component comprises a petroleumpitch, a coal-tar pitch, a liquefied coal oil, or a combination thereof.25. The method of claim 16, wherein said mixture comprises a syntheticresin and said synthetic resin comprises a phenol resin, a furan resin,a furfural resin, a divinyl benzene resin, a urea resin, or acombination thereof.
 26. The method of claim 16, wherein saidcarbonaceous particles comprise 100 parts by weight carbon black andsaid mixture further comprises from about 10 to about 500 parts byweight said synthetic resin, pitch component, or both.
 27. The method ofclaim 16, wherein said carbonaceous particles comprise carbon blackparticles having a ratio L_(min)/L_(max) of a minor axis diameterL_(min) to a major axis diameter L_(max) of from about 0.95 to about1.0, a particle diameter of from about 2 to about 200 μm, a specificsurface area of from about 10 to about 650 m²/g, a total microporevolume of from about 0.3 to about 2.0 ml/g, and a V_(0.5)/V_(1.0) ratioof about 0.4 or smaller wherein V_(0.5) is the gas adsorption volume ata relative pressure P/P₀ of 0.5 and V_(1.0) is the nitrogen gasadsorption volume at a relative pressure P/P₀ of about 1.0 at nitrogengas adsorption isotherm.
 28. The method of claim 16, wherein saidcarbonaceous particles are substantially spherical.
 29. The method ofclaim 16, wherein said carbonaceous particles are aggregates comprisinga carbon phase and a silicon-containing species phase.
 30. The method ofclaim 16, wherein said granulating comprises a spray granulation or anemulsion granulation method.
 31. The method of claim 16, wherein saidcarbonaceous particles comprise carbon black having an average particlediameter of from about 12 to about 40 nm and said mixing comprisesmixing 100 parts by weight said carbon black with about 10 to about 250parts by weight of said synthetic resin, pitch component, or both. 32.The method of claim 16, wherein said carbonaceous particle comprisescarbon black having an average particle diameter of from about 12 toabout 30 nm, a specific surface area of from about 80 to about 250 m²/g,and a DBP oil adsorption of from about 80 to about 200 ml/100 g.
 33. Themethod of claim 16, wherein said granulating comprises granulating saidmixture by spray granulation or emulsion granulation to obtain granuleswhose ratio L_(min)/L_(max) of a minor axis diameter L_(min) to a majoraxis diameter L_(max) is from about 0.90 to about 1.0.
 34. The method ofclaim 16, wherein said attaching comprises reacting said granules with adiazonium salt.
 35. The method of claim 16, wherein said organic groupcomprises an ionic group or an ionizable group.
 36. (canceled)
 37. Amethod of making carbonaceous particles-containing granules comprising:mixing carbonaceous particles having attached at least one organic groupwith: at least one synthetic resin, pitch component, or a mixturethereof; and at least one solvent, to form a mixture; granulating saidmixture to form granules; and carbonizing said granules.
 38. The methodof claim 37, further comprising attaching a second organic group to saidgranules after carbonizing, wherein said second organic group is thesame or different from said organic group. 39-43. (canceled)
 44. Agranulated carbonaceous product comprising carbonaceous particles and atleast one uncarbonized binder, produced by the process of: mixing thecarbonaceous particles with at least one binder and at least onesolvent; granulating said mixture to form granules; and heating saidgranules at a temperature below the carbonaceous temperature of thebinder to form said granulated carbonaceous product.
 45. The granulatedcarbonaceous product of claim 44, wherein said carbonaceous particleshave attached at least one organic group.
 46. (canceled)